CN1325950A - Nm-class composite detergent and its preparing process - Google Patents
Nm-class composite detergent and its preparing process Download PDFInfo
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Abstract
A nm-class composite detergent is prepared from nm-class inorganic non-metal mineral, nm-class inorganic antibacterial composition and surfactant by nm compounding technology. Its advantages include non-phosphorus detergent, high detergency, antibacterial function, no environmental pollution, and strong adsorption power.
Description
The invention belongs to the daily-use chemical industry technical field, relate more specifically to contain the detergent composition of the natural inorganic non-metallic minerals of the stratiform handled through nanometer composite technology or pore passage structure with nanoscale, relate in particular to and utilize nanometer composite technology, make the non-phosphide detergent that contains compositions such as the nonmetal nano-mineral of natural inorganic, nano composite inorganic antiseptic-germicide.
At present, the household laundry powder annual production of China has reached more than 300 ten thousand tons, 2.5 kilograms of year quantity per capitas, and actual capacity also wants big many.But the washing powder common technique content of China is few at present, and technical value added is low, and 90% is phosphorous washing powder.No phosphorus powder only accounts for 10%.Phosphorous washing powder can cause serious pollution to rivers,lakes and seas, major cause is after the tripoly phosphate sodium STPP in the washing powder dissolves in water, cause the phosphorus content of water to increase, make water body eutrophication occur, algae and planktonic organism breed in a large number, cause water oxygen level to descend the water quality severe exacerbation, cause all death of hydrocoles such as fishes and shrimps, people and animals' unable to drink is used.Phenomenons such as the inland lake water quality deterioration that China recent years occurs, coastal waters red tide, all relevant therewith.In view of the side effect of phosphorous washing powder to environment, as far back as the seventies, developed countries has just stipulated that synthetic detergent should limit or ban use of phosphoric acid salt.Realizing that at first all the country of no phosphatization is Switzerland (1986), secondly is Canada (1988).And China still is unrealized now, and the road of taboo phosphorus is also very long.Though relevant implementing regulations have been put into effect in many cities, are not effectively carried out yet, phosphorous washing powder is still in occupation of the most market share.
It is why difficult that synthetic detergent all realizes not having phosphatization, mainly is because do not find suitable phosphate builders surrogate.In more existing surrogates, the poor effect that has, the microbic resolvability that has is bad, the cost height that has.Even, on the understanding of consumption, composition, function, still there is difference to some materials of widespread usage.But the no phosphatization of washing powder is unshakable direction, also is the project of vital and lasting importance of protecting environment, benefiting the nation and the people.
The development of nanotechnology has been opened up new space for the technical progress of synthetic detergent, utilizes the new features of nano material can realize the multifunction of washing composition.Purpose of the present invention utilizes nanotechnology to develop a kind of novel, environment amenable free phosphate detergent composition exactly, strengthens the detersive power and the cleaning capacity of washing composition, realizes antibacterial, sterilizing function simultaneously, makes fabric obtain profound cleaning.
Synthetic detergent mainly comprises two kinds of compositions: tensio-active agent and washing assistant, the function of tensio-active agent are wetting, infiltration, emulsification, dispersion, foaming, viscosity reduction etc., are the main components in the washing composition, can be water-soluble fully.The function of washing assistant is to improve and improve the over-all properties of synthetic detergent, mainly comprises:
1, improve scourability: can be by synergy with the surface-active substance synergy, hardness ions in chelating or the precipitation water is simultaneously stablized the pH value of washings;
2, dirt on the fiber of various character and the fabric is carried out wash-out, comprise physical action and chemical action;
3, the dirt all-the-time stable with desorption is dispersed in the scrub raffinate, anti-soil redeposition;
4, booster action as perfuming, be easy to granulating and forming, reduces cost etc.
Of the present inventionly mainly be intended that:
1, utilize nanotechnology, washing assistant is carried out retrofit, hardness ions in the quick chelating water, and possess good low-temperature performance;
2, utilize the active and ultra-fine characteristics of nanoparticle, promote organic greasy dirt and inorganic foulants particulate wash-out, improve detersive power;
3, utilize the high-specific surface area of nano-mineral, colored ion and dirt particles in the absorption scrub raffinate;
4, will have nano material antibiotic, automatic cleaning action and introduce in the washing composition, realize that the profound level that is washed fabric cleans, keeps a public place clean; Realize the green discharging of scrub raffinate.
The contriver finds, through the containing aluminium or the natural non-metallic minerals of magniferous clay class and if you would take off stone family layered silicate, wilkinite, sepiolite group mineral etc. and can be used as washing assistant and be used for detergent composition of nano combined processing, can improve the detersive power of washing composition greatly.
According to embodiment of the present invention, detergent composition of the present invention comprises tensio-active agent, through natural inorganic non-metallic minerals and other washing assistant of composite Nano intercalation processing.Tensio-active agent and other washing assistant can be those that use always in the art, it is selected from anionic (as LAS, ABS etc.), cationic (as the dodecyl ammonium oxide) and nonionic surface active agent (as AEO, the mixture of one or more BV) and in the compound.The nonmetal nano-mineral of natural inorganic is the clay class natural mineral that contains aluminium or magnesium, if you would take off stone family layered silicate, sepiolite group mineral etc.Specific examples is aluminium montmorillonite, wilkinite, sepiolite, attapulgite etc.Other washing assistant is selected from one or more in the agent of resistive connection group, alkaline promoting agent, calcium ions and magnesium ions suspension agent, the soil-suspending agent etc., does not preferably comprise phosphorated washing assistant such as tripoly phosphate sodium STPP.
The natural inorganic non-metallic minerals that the present invention selects, mainly comprise two kinds of structures: a kind of is that 0.4-2 nanometer, space are that the silicate lamella of 0.5-2 nanometer is formed by thickness, another kind of is 0.4-2 nanometer interstitial channels by being uniform-distribution with the aperture, and diameter is that the mineral fibre of 10-200 nanometer is formed.The inorganic non-metallic mineral of these two kinds of structures have great specific surface area, have specific nano functional in the aqueous solution.For in washing powder, using, they must pass through nano combined processing, concrete grammar comprises ion-exchange etc. between intercalation between nanometer layer, nanometer, this processing can by under heated condition by ion exchange, realize as cationic exchange, for example can referring to polymer circular (2000,2,18-25), the ion-exchange techniques announced among the open CN 1250064A of Chinese patent.Purpose be with have washing, emulsification, hardness ions sequestering action composition be inserted in nanometer lamella or the passage, when washing, discharge, by acting synergistically with tensio-active agent, the high-effective cleansing effect is played in the wash-out and the dispersion of solid particulate and oily dirt on the promotion fabric.Can prevent also that simultaneously calcium ion and magnesium ion from depositing to fabric and fiber surface, helps to keep the feel of fabric.
At first, nanometer lamella and passage, can pass through Combined Processing, adsorb chelating ion and tensio-active agent that a large amount of softening waters are used, when washing by friction and ion-exchange, except the hardness ions in the chelating water rapidly, can also be delivered to the cleaning function zone apace, by acting synergistically with surface-active substance, soil-removing action is efficiently played in the wash-out and the dispersion of solid particulate and oily dirt on the promotion fabric; Secondly, have the nanoparticle suspension particle of electric charge, can with produce intensive attached to the greasy dirt on the fabric and solid dirt particles and interact, under the mechanical force in washing process, can promote the quick wash-out of dirt; At last, nano material with very big specific surface area, when in water, suspending, can effectively adsorb colored ion and dirt particles in the scrub raffinate, alleviated the damage of mineral ion to fabric, the throw out that also can prevent calcium ion and magnesium ion simultaneously deposits to fabric and fiber surface, has reduced the ash-deposition amount on the fabric, also helps to keep the feel of fabric.
The nonmetal nano-mineral of natural inorganic must could be realized the nano material function that it is specific through nano combined processing.Processing comprises the steps: at first natural mineral to be cleaned ore dressing, 80-300 ℃ of oven dry down, reaches required tissue morphology, structure and composition.Then pretreated natural mineral is carried out between above-mentioned nanometer ion exchange treatment between intercalation, nanometer.But preferably, before oven dry, in acid solution or alkali lye, soak and carry out activation treatment.Acid solution can be common acid solution such as salpeter solution, hydrochloric acid soln, sulphuric acid soln, and alkali lye can be sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution etc.Under strong acid, alkaline situation, preferred concentration is no more than 50%.
In a preferred embodiment of the invention, detergent composition of the present invention also comprises the nanometer particle antiseptic-germicide, the nanometer particle antiseptic-germicide has significant restraining and sterilizing bacteria effect, particle size range is the 5-90 nanometer, and nano antibacterial agent of the present invention is selected from one or more mixture of rare earth element and compound (as cerium oxide, lanthanum trioxide etc.), inorganic fungicide (as silver salt, zinc salt etc.), organic bactericide (as thiazole etc.) and photochemical catalysis material (as titanium dioxide, zinc oxide etc.).They have antibacterial, germicidal action in solid or liquid state, also can play effective catalyticing decomposition action to organic dirt, for bringing into play the antiseptic-germicide effect to greatest extent.Antiseptic-germicide is nontoxic to human body, and the nano antibacterial agent that remains on the clothing can be penetrated into fibrous inside, plays profound restraining and sterilizing bacteria effect.Nanometer particle antiseptic-germicide of the present invention can prepare with common sol-gel method.
In a preferred embodiment of the present invention, detergent composition of the present invention comprises:
Tensio-active agent 10～40wt%
Treated natural inorganic non-metallic minerals 1～40wt%
Nanometer particle antiseptic-germicide 0.1～25wt%
Alkalescence promoting agent 5～40wt%
Calcium ions and magnesium ions sequestrant 5～60wt%
SYNTHETIC OPTICAL WHITNER 1～5wt%
Soil-suspending agent 0～20wt%
Agent 1～the 5wt% of resistive connection group
White dyes 0.1～1wt%
Weighting material 0～30wt%
Spices 0～0.1wt%
Wherein tensio-active agent can be selected from anionic (as LAS, ABS etc.), cationic (as the dodecyl ammonium oxide) and nonionic surface active agent (as AEO, the mixture of one or more BV) and in the compound.The natural inorganic non-metallic minerals can be the clay class natural mineral that contains aluminium or magnesium, if you would take off stone family layered silicate (swelling great soil group), sepiolite group mineral (attapulgite) etc., and treatment process as mentioned above.Nano antibacterial agent has significant restraining and sterilizing bacteria effect, particle size range is the 5-90 nanometer, and the nanometer particle antiseptic-germicide is selected from one or more mixture of rare earth element and compound (as cerium oxide, lanthanum trioxide etc.), inorganic fungicide (as silver salt, zinc salt etc.), organic bactericide (as thiazole etc.) and photochemical catalysis material (as titanium dioxide, zinc oxide etc.).The alkalescence promoting agent is selected from alkaline matters such as yellow soda ash, water glass.The calcium ions and magnesium ions sequestrant is selected from materials such as 4A zeolite, laminated crystalline silicic acid disodium (SKS-6), yellow soda ash, water glass.The agent of resistive connection group for example is selected from sodium xylene sulfonate, sodium sulfosuccinate etc.SYNTHETIC OPTICAL WHITNER can be any SYNTHETIC OPTICAL WHITNER that is used for washing powder, and spices is the spices that is generally used for washing powder.Soil-suspending agent can be any washing powder that is used for washing powder, and white dyes can be common any white dyes that is used for washing powder, and weighting material can be any filler that is used for washing powder, as sodium sulfate etc.
At last, the composition of various processing mixed activate, carry out long activation treatment at 20-150 ℃, product drying drying, spray-drying process or agglomeration technique after the activation are made washing powder.
Present technique have technology advanced person, cost low, be easy to advantages such as existing production technique undergo technological transformation.The washing composition of making is without phosphorus, efficient, strong detergency, effective sterilizing cleaning, environmental sound, high adsorption capacity.
The present invention compares with existing other non-phosphide detergent production technologies, has following different characteristics:
1, adopted nano intercalated compounding technology, by nonmetal nano mineral materials of natural inorganic and surface-active substance synergistic function, soil-removing action is efficiently played in the wash-out and the dispersion of solid particulate and oily dirt on the promotion fabric.
2, utilize the washing auxiliary detergent composition of nanotechnology processing, fast hardness ions in the chelating water.
3, utilize the high-specific surface area of nano-mineral, colored ion and dirt particles in the absorption scrub raffinate;
4, will have nano material antibiotic, automatic cleaning action and introduce in the washing composition, play the restraining and sterilizing bacteria effect, can realize that the profound level that is washed fabric cleans, keeps a public place clean and the green of scrub raffinate is discharged.
Below in conjunction with embodiment the present invention is described.It should be noted that these embodiment only are part preferred embodiments of the present invention, they are not to be used for limiting the scope of the invention.
Embodiment 1
Get natural montmorillonite, after cleaning, in 10% hydrochloric acid soln, soaked 20 minutes, then 100 ℃ of oven dry down.Product after the oven dry carries out nano intercalated Combined Processing by the ion exchange at heated condition.Product after the processing mixes with other composition in ratio listed in the table 1, wherein anion surfactant is a Sodium dodecylbenzene sulfonate in the table, nonionogenic tenside is dodecyl alcohol polyoxyethylene (a 9) ether, and nano inorganic antimicrobial agent is nano level cerium oxide, zinc nitrate and 1: 1: 1 mixture of titanium dioxide.Kept about 72 hours the spray-dried then washing powder of making down at 50 ℃.
Embodiment 2
Get natural attapulgite, after cleaning, in 10% sodium hydroxide solution, soak and carried out activation treatment in 30 minutes.120 ℃ of oven dry down, the product after the oven dry carries out nano combined processing by the ion exchange at heated condition then.Product after the processing mixes with other composition in the listed ratio of table 1, wherein the anion surfactant in the table is a sodium lauryl sulphate, nonionogenic tenside is dodecyl phenol polyethenoxy (a 10) ether, and nano inorganic antimicrobial agent is nano level cerium oxide and 1: 1 mixture of titanium dioxide.Mix the back and kept about 48 hours down at 30 ℃, the drying drying is made washing powder then.
Embodiment 3
Present embodiment is the concentrated detergent powder prescription.Get natural montmorillonite, after cleaning, in 5% hydrochloric acid soln, soaked 20 minutes, then 100 ℃ of oven dry down.Product after the oven dry carries out nano intercalated Combined Processing by the ion exchange at heated condition.Product after the processing mixes with other composition in ratio listed in the table 1, wherein anion surfactant is a Sodium dodecylbenzene sulfonate in the table, nonionogenic tenside is dodecyl alcohol polyoxyethylene (a 9) ether, and nano inorganic antimicrobial agent is nano level cerium oxide, silver chloride, thiazole and titanium dioxide 1: 1: 1: 1 mixture.Mix the back and kept about 72 hours down at 50 ℃, the drying drying is made washing powder then.Nanometer washing powder formulation examples among table 1 the present invention
The relevant performance data of table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The anion surface activity thing | 15wt％???? | 6wt％ | 13wt％ |
| The non-ionic surface active thing | 5wt％???? | 6wt％ | 10wt％ |
| Natural inorganic non-metallic minerals (handling the back) | 10wt％ | 15wt％ | 5wt％ |
| The 4A zeolite | 25wt％ | 40wt％ | 30wt％ |
| Metasilicic acid is received | 5wt％ | 5wt％ | 5wt％ |
| Soda ash | 10wt％ | 5wt％ | 10wt％ |
| Nano antibacterial agent | 2wt％ | 2wt％ | 2wt％ |
| Fluorescent bleaches | 0.2wt％ | 0.2wt％ | 0.2wt％ |
| Sodium xylene sulfonate | 2wt％ | 2wt％ | 2wt％ |
| Sodium sulfosuccinate | 2wt％ | 2wt％ | 2wt％ |
| Laminated crystalline silicic acid disodium (SKS-6) | 10wt％ | 5wt％ | 8wt％ |
| SYNTHETIC OPTICAL WHITNER | 5wt％ | 5wt％ | 5wt％ |
| Water | Surplus | Surplus | Surplus |
| Detersive power ratio | The antiredeposition performance | The calcium ion sequestering power | The magnesium ion sequestering power | Foaming properties | |
| National standard | ≥1.0 | ≤3 | ≤130mm | ||
| Embodiment 1 | ?1.7 | ?2.0 | ＞98％ | ＞80％ | 100mm |
| Embodiment 2 | ?1.4 | ?2.5 | ＞95％ | ＞90％ | 50mm |
| Embodiment 3 | ?1.6 | ?2.0 | ＞95％ | ＞90％ | 80mm |
Washing composition of the present invention as can be seen from the above results has good detersive power, antiredeposition performance, calcium ion sequestering power, magnesium ion sequestering power and foaming properties.
Appendix: relevant patent: 1. application number 96180171, notification number 1213991: raising contains active method 2. application numbers 97116447 of zeolite granular solids, notification number 1211537: a kind of preparation method's 3. application numbers 98100064 of fine-crystal model A zeolite, notification number 1224051: phosphate-free soil-release antibacterial detergent and preparation method thereof 4. application numbers 90105835, notification number 1047333: non-phosphide detergent 5. application numbers 95106991, notification number 1138630: utilize the 4A zeolite to produce technology 6. application numbers 89103674 of non-phosphide detergent, notification number 1039262A: nontoxic (phosphate-free and aluminum-free) washing powder 7. application numbers 97105931.4, notification number CN1168917A: activation sepiolite constituent and preparation method thereof 8.U.S.Patent6020293, Appl.No.:095720 (1998): Antimicrobial compositions9.U.S.Patent6015816, Appl.No.:807140 (1997): Enzymatic detergent composition and method foe detgrading and removing bacterial cellulose10.U.S.Patent 5658870, Appl.No.:701245 (1996): Composition of super molecule
It is female etc. that active solid cleaning Lu agent11. builds, the formation mechanism and the performance of epoxy/clay nanocomposites, polymer circular, 2000 (6), 2,18-2512. He Peng, Zhao Antai, the nanometer composite technology in the polymer modification, the polymer circular, 2001 (2), 1,74-81
Claims (9)
1, a kind of detergent composition, it is characterized in that it contains the laminate structure with nanoscale handled through nanometer composite technology or the natural inorganic non-metallic minerals of pore passage structure, wherein said natural inorganic non-metallic minerals is to have containing aluminium (if you would take off stone family layered silicate, wilkinite) or containing the clay class natural mineral of magnesium (sepiolite group mineral, attapulgite) of the laminate structure of nanoscale or pore passage structure.
2, the composition of claim 1, it also comprises tensio-active agent and other washing assistant.
3, claim 1 or 2 composition, it is characterized in that it also comprises the nanometer particle antiseptic-germicide, described antiseptic-germicide is selected from one or more mixture of nano-scale rare earth element and compound (as cerium oxide, lanthanum trioxide etc.), nano grade inorganic sterilant (as silver salt, zinc salt etc.), nano level organic bactericide (as thiazole etc.) and nano level photochemical catalysis material (as titanium dioxide, zinc oxide etc.).
4, a kind of detergent composition, it comprises following component:
Tensio-active agent 10～40wt%
Natural inorganic non-metallic minerals 1～40wt%
Nanometer particle antiseptic-germicide 0.1～25wt%
Alkalescence promoting agent 5～40wt%
Calcium ions and magnesium ions sequestrant 5～60wt%
SYNTHETIC OPTICAL WHITNER 1～5wt%
Soil-suspending agent 0～20wt%
Agent 1～the 5wt% of resistive connection group
White dyes 0.1～1wt%
Weighting material 0～30wt%
Spices 0～0.1wt%
5, according to the composition of claim 4, wherein the natural inorganic non-metallic minerals is the clay class natural mineral that contains aluminium (if you would take off stone family layered silicate, wilkinite) or contain magnesium (sepiolite group mineral, attapulgite).
6, according to the composition of claim 4, wherein the nanometer particle antiseptic-germicide is selected from one or more mixture of nano-scale rare earth element and compound (as cerium oxide, lanthanum trioxide etc.), nano grade inorganic sterilant (as silver salt, zinc salt etc.), nano level organic bactericide (as thiazole etc.) and nano level photochemical catalysis material (as titanium dioxide, zinc oxide etc.).
7, according to the composition of claim 4, its neutral and alkali promoting agent is selected from alkaline matters such as yellow soda ash, water glass; The calcium ions and magnesium ions sequestrant is selected from one or more in 4A zeolite, laminated crystalline silicic acid disodium (SKS-6), yellow soda ash, the water glass; The agent of resistive connection group is selected from one or both in sodium xylene sulfonate, the sodium sulfosuccinate; SYNTHETIC OPTICAL WHITNER is any SYNTHETIC OPTICAL WHITNER that can be used for washing powder; Spices is the spices that is generally used for washing powder; Soil-suspending agent is any suspension agent that can be used for washing powder; White dyes can be common any white dyes that is used for washing powder; Weighting material can be any filler that is used for washing powder, as sodium sulfate.
8, each method for compositions among the preparation claim 4-7 comprises:
1. the natural inorganic non-metallic minerals is cleaned, then oven dry;
2. the nonmetal nano-mineral of above-mentioned pretreated natural inorganic being carried out nanometer composite technology by ion exchange in heated condition handles;
3. the nonmetal nano-mineral of the natural inorganic that will handle and other composition thorough mixing, and under 20-150 ℃, activate together;
4. washing powder is made in product drying, spraying drying or the agglomeration after the activation.
9, method according to Claim 8, the pre-activated of wherein carrying out before oven dry in acid solution or alkali lye is handled.
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| CN100464856C (en) * | 2003-10-15 | 2009-03-04 | 托尔萨公司 | Method of preparing metallic nanoparticles and materials thus obtained |
| CN102040954A (en) * | 2009-10-12 | 2011-05-04 | 上海洗霸科技有限公司 | Cerium oxide additive, inhibitive glycol antifreeze solution and diluent thereof |
| CN102327195A (en) * | 2011-10-10 | 2012-01-25 | 王凤智 | Multifunctional attapulgite cleaning block |
| CN103103043A (en) * | 2012-12-19 | 2013-05-15 | 隋丽梅 | Outer wall cleaning powder composition of green building with self-cleaning function |
| CN103214903A (en) * | 2013-03-27 | 2013-07-24 | 北京鸿业润升科技有限公司 | Peelable nano-grade decontamination coating |
| CN103564196A (en) * | 2013-11-15 | 2014-02-12 | 苏州大学 | Additive for improving bombyx mori yield |
| CN103860589A (en) * | 2014-03-14 | 2014-06-18 | 沈阳药科大学 | Rare-earth compound with antibacterial anti-fungus functions |
| CN104194972A (en) * | 2014-08-06 | 2014-12-10 | 明光市国星凹土有限公司 | Modified attapulgite washing auxiliary detergent and preparation method thereof |
| CN105420000A (en) * | 2015-12-18 | 2016-03-23 | 国网山东高唐县供电公司 | Care agent for whiteboard for electric power training and preparation method of care agent |
| CN105623868A (en) * | 2015-12-28 | 2016-06-01 | 广东都市丽人实业有限公司 | Nano-silver washing solution and preparation method thereof |
| CN106833915A (en) * | 2017-01-17 | 2017-06-13 | 美丽神话（武汉）科技有限公司 | A kind of efficient, laundry sheet of rapid cleaning |
| CN106957738A (en) * | 2017-04-11 | 2017-07-18 | 安徽省明美矿物化工有限公司 | A kind of bleaching agent containing attapulgite and preparation method thereof |
| CN109112003A (en) * | 2018-09-28 | 2019-01-01 | 广州市加茜亚化妆品有限公司 | A kind of use in dishwasher washs solidifying pearl and preparation method |
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| CN100464856C (en) * | 2003-10-15 | 2009-03-04 | 托尔萨公司 | Method of preparing metallic nanoparticles and materials thus obtained |
| CN102040954A (en) * | 2009-10-12 | 2011-05-04 | 上海洗霸科技有限公司 | Cerium oxide additive, inhibitive glycol antifreeze solution and diluent thereof |
| CN102040954B (en) * | 2009-10-12 | 2013-10-09 | 上海洗霸科技股份有限公司 | Inhibitive glycol antifreeze solution comprising additive |
| CN102327195A (en) * | 2011-10-10 | 2012-01-25 | 王凤智 | Multifunctional attapulgite cleaning block |
| CN102327195B (en) * | 2011-10-10 | 2013-03-27 | 王凤智 | Multifunctional attapulgite cleaning block |
| CN103103043A (en) * | 2012-12-19 | 2013-05-15 | 隋丽梅 | Outer wall cleaning powder composition of green building with self-cleaning function |
| CN103214903A (en) * | 2013-03-27 | 2013-07-24 | 北京鸿业润升科技有限公司 | Peelable nano-grade decontamination coating |
| CN103564196A (en) * | 2013-11-15 | 2014-02-12 | 苏州大学 | Additive for improving bombyx mori yield |
| CN103860589A (en) * | 2014-03-14 | 2014-06-18 | 沈阳药科大学 | Rare-earth compound with antibacterial anti-fungus functions |
| CN104194972A (en) * | 2014-08-06 | 2014-12-10 | 明光市国星凹土有限公司 | Modified attapulgite washing auxiliary detergent and preparation method thereof |
| CN105420000A (en) * | 2015-12-18 | 2016-03-23 | 国网山东高唐县供电公司 | Care agent for whiteboard for electric power training and preparation method of care agent |
| CN105623868A (en) * | 2015-12-28 | 2016-06-01 | 广东都市丽人实业有限公司 | Nano-silver washing solution and preparation method thereof |
| CN106833915A (en) * | 2017-01-17 | 2017-06-13 | 美丽神话（武汉）科技有限公司 | A kind of efficient, laundry sheet of rapid cleaning |
| CN106957738A (en) * | 2017-04-11 | 2017-07-18 | 安徽省明美矿物化工有限公司 | A kind of bleaching agent containing attapulgite and preparation method thereof |
| CN109112003A (en) * | 2018-09-28 | 2019-01-01 | 广州市加茜亚化妆品有限公司 | A kind of use in dishwasher washs solidifying pearl and preparation method |
| CN114403737A (en) * | 2022-01-20 | 2022-04-29 | 北京国家速滑馆经营有限责任公司 | Cleaning method suitable for curtain wall |
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